BRPI0808471B1 - aqueous dispersion, use of aqueous dispersions, process for producing multilayer sheet substrates, multilayer sheet substrate, use of multilayer sheet substrates, and car interior panels, shoes, textiles or furniture . - Google Patents

Description

(54) Title: WATER DISPERSION, USE OF Aqueous DISPERSIONS, PROCESS FOR THE PRODUCTION OF MULTIPLE LAYER SHEET SUBSTRATES, MULTIPLE LAYER SHEET SUBSTRATE, USE OF MULTIPLE LAYERED SUBSTRATES, LAMPS, LAMPS, LAMPS TEXTILES OR FURNITURE PIECE.

(51) lnt.CI .: C08G 18/08; C08G 18/28; C08G 18/32; C08G 18/34; C08G 18/38; C08G 18/42; C08G 18/66; C08G 18/72; C08G 18/79; C09D 175/04; CMC 11/00; C08K 7/22; D06M 15/564; C08L 75/04; C08L 83/00 (30) Unionist Priority: 03/21/2007 EP 07104557.9, 03/26/2007 EP 07104899.5 (73) Holder (s): BASF SE (72) Inventor (s): NIDIA BUSTOS; JÜRGEN WEISER (85) National Phase Start Date: 09/09/2009 “WATER DISPERSION, USE OF WATER DISPERSIONS, PROCESS FOR THE PRODUCTION OF MULTI-LAYER SHEET SUBSTRATES, MULTI-LAYER SHEET SUBSTRATE, SUBSTRATE TYPE SUBSTRATE MULTIPLE LAYERS, AND,

CAR INTERIOR PANELS, SHOES, TEXTILES OR FURNITURE PIECE ”

The present invention relates to aqueous dispersions comprising (a) at least one polyurethane, (b) at least one compound of the general formula I a or I b

O

Ia I b where R, R and R can be identical or different and are selected from Α’-ΝΟΟ and A ^ NH-CO-X, where

A ¹ is a spacer having 2 to 20 carbon atoms and X is selected from O (AO) _X R ⁴ ,

AO is C ₂ -C ₄ alkylene oxide, x is an integer in the range 1 to 50 and R ⁴ is selected from hydrogen and C 1 -C ₃₀ alkyl, (C) and at least one silicone compound having reactive groups.

Aqueous silicone-containing dispersions have numerous applications. Thus, they are used, for example, to impart water repellency to leaf-like substrates, such as, for example, textiles or leather. A specific application is leather coating with the help of a reverse roller coating process described, for example, in WO 05/47549. The top layer with which the leather is coated plays a decisive role for tactile properties.

DE 20 2006 007 957 UI describes that cured leathers can be produced using silicone dispersions that have particles having an average diameter from 3 pm to 13 pm and that are added to a polyurethane dispersion that is applied as a top layer by the coating process of reverse roller to the leather to be coated. The firmness, in particular the permanent handling firmness, of leathers coated in this way can, however, be further improved. In addition, the usefulness of the matrices can still be improved.

In this way, the aim was to provide silicone dispersions that are suitable for coating substrates, in particular by the reverse roller coating process. In addition, it is an objective to provide coated substrates having good firmness, in particular friction firmness and good handling. In addition, it was the aim to provide a process for the production of coated substrates that gives the previously mentioned coated substrates and can be carried out advantageously.

In this way, the aqueous dispersions defined at the beginning were found.

Aqueous dispersions according to the invention comprise (A) at least one polyurethane which is also referred to as polyurethane (A) in the context of the present invention.

Polyurethane (A) is preferably a thermoplastic polyurethane. Thermoplastic polyurethanes (also referred to as TPU in brief) and dispersions prepared therefrom are known as such.

Polyurethanes (A) are generally known and commercially available and generally consist of a soft phase comprising relatively high molecular weight polyhydroxy compounds, for example, comprising polyester or polyether segments, and a hard urethane phase, formed of low chain extenders. molecular weight and di- or polyisocyanates.

Processes for the preparation of polyurethanes (A) are generally known. In general, polyurethanes (A) are prepared by reacting (a) isocyanates, preferably diisocyanates, (b) with reactive compounds with isocyanates, usually having a molecular weight (M _w ) of 500 to 10,000 g / mol, preferably 500 to 5,000 g / mol, particularly preferably 800 to 3,000 g / mol, and (c) chain extenders having a molecular weight of 50 to 499, if appropriate in the presence of (d) catalysts (e) and / or customary additives.

In the following, the starting components and processes for preparing the preferred polyurethanes (A) are described by way of example. The components (a), (b), (c) and, if appropriate, (d) and / or (e) normally used in the preparation of polyurethanes are described below by way of example:

Isocyanates (a) used can generally be known aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, for example, tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate,

1.5- 2-methylpentamethylene diisocyanate, 2-ethylbutylene 1,4-diisocyanate,

1.5-pentamethylene diisocyanate, butylene 1,4-diisocyanate, 3,3.5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis (isocyanatomethyl) cyclohexane ( HXDI), 1,4 — cyclohexane diisocyanate, 2,4-and / or 2,6-diisocyanate of 1-methylcyclohexane and / or 4,4'-, 2,4'- and 2,2'-diisocyanate of dicyclohexylmethane , Diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), naphthylene 1,5-diisocyanate (NDI), 2,4- and / or 2,6-diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethylbiphenyl diisocyanate, 1,2-diphenylethane diisocyanate and / or phenylene diisocyanate. 4,4'-MDI is preferably used. Aliphatic diisocyanates, in particular hexamethylene diisocyanate (HDI), are also preferred, and aromatic diisocyanates, such as diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), and mixtures of the aforementioned isomers are particularly preferred.

The generally known compounds reactive with isocyanate can be used as compounds (b) reactive with isocyanates, for example, polyesterols, polyetherols and / or polycarbonatodiols, which are usually also summarized by the term "polyols", having molecular weights (Mw) in the range of 500 to 8,000 g / mol preferably from 600 to 6,000 g / mol, in particular from 800 to 3,000 g / mol, and preferably an average functionality with respect to isocyanates from 1.8 to 2.3, preferably from 1.9 to 2.2 , in particular 2. Polyetherpolyols are preferably used, for example, those based on commonly known starting substances and routine alkylene oxides, for example, ethylene oxide, 1,2-propylene oxide and / or 1,2- butylene, preferably polyetherols based on polyoxytetramethylene (poly-THF), 1,2-propylene oxide and ethylene oxide. Polyetherols have the advantage that they have greater hydrolysis strength than polyesterols and are preferred as a component (b), in particular for the preparation of soft polyurethanes (A ¹ ).

In particular, aliphatic polycarbonatodiols, for example, 1,4-butanediol polycarbonate and 1,6-hexanediol polycarbonate, can be mentioned as polycarbonatodiols.

Polyesterdiols that can be mentioned are those that can be prepared by polycondensation of at least one primary diol, preferably at least one primary aliphatic diol, for example, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol or particularly preferably 1,4-dihydroxymethylcyclohexane (as a mixture of isomers) or mixtures of at least two of the aforementioned diols, on the one hand, and at least one dicarboxylic acid, preferably at least two dicarboxylic acids, or their anhydrides, on the other hand. Preferred dicarboxylic acids are aliphatic dicarboxylic acids, such as adipic acid, glutaric acid, succinic acid, and aromatic dicarboxylic acids, such as, for example, phthalic acid and in particular isophthalic acid.

Polyetherols are preferably prepared by an addition reaction of alkylene oxides, in particular ethylene oxide, propylene oxide or mixtures thereof, with diols, such as, for example, ethylene glycol, 1,2-propylene glycol, 1,2 -butylene glycol, 1,4-butanediol, 1,3propanediol, or with triols, such as, for example, glycerol, in the presence of highly active catalysts. Such highly active catalysts are, for example, cesium hydroxide and double metal cyanide catalysts, also referred to as DMC catalysts. A frequently used DMC catalyst is zinc hexacyanocobaltate. The DMC catalyst can be left in the polyetherol after the reaction, but is preferably removed, for example, by sedimentation or filtration.

Instead of a polyol, it is also possible to use mixtures of different polyols.

To improve dispersibility, one or more diols or diamines having a carboxyl group or sulfo group (b '), in particular alkali metal or ammonium salts of 1,1-dimethylolbutanoic acid, 1,1dimethylolpropionic acid or

O

H can also be used proportionally as compounds (b) reactive with isocyanates.

Chain extenders (c) used are aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds known per se and having a molecular weight of 50 to 499 g / mol and at least two functional groups, preferably compounds having exactly two functional groups per molecule, for example, diamines and / or alkanediols having 2 to 10 carbon atoms in the alkylene radical, in particular 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and / or di-, tri-, tetra-, penta- , hexa-, hepta-, octa-, nona- and / or decaalkylene glycols having 3 to 8 carbon atoms per molecule, preferably corresponding oligo- and / or polypropylene glycols, it is also possible to use mixtures as chain extenders (c).

Components (a) to (c) are particularly preferably difunctional compounds, i.e., diisocyanates (a), difunctional polyols, preferably polyetherols (b), and difunctional chain extenders, preferably diols.

Suitable catalysts (d) that accelerate, in particular, the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the synthesis components (b) and (c) are tertiary amines known per se, such as, for example, triethylamine, dimethylcyclohexylamine, N-methylmorpholine, Ν, Ν'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo [2.2.2] octane (“DABCO”) and similar tertiary amines and, in particular, organic metal compounds such as titanic acid esters, iron compounds, such as, for example, iron (III) acetylacetonate, tin compounds, for example, tin diacetate, tin dioctanoate, tin dilaurate and the dialkyl tin salts of aliphatic carboxylic acids, such as dibutyl tanner diacetate, tin dibutyldilaurate or the like. Catalysts are normally used in amounts of 0.0001 to 0.1 part by weight per 100 parts by weight of component (b).

In addition to catalysts (d), auxiliaries and / or additives (e) can also be added to components (a) to (c). Blowing agents, anti-blocking agents, active surface substances, fillers, for example, fillers based on nanoparticles, in particular fillers based on CaCC> 3, in addition, nucleating agents, lubricants, dyes and pigments, antioxidants, for example For example, against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers, metal deactivators can be mentioned by way of example. In a preferred embodiment, component (e) also includes hydrolysis stabilizers, such as, for example, polymeric and low molecular weight carbodiimides. The soft polyurethane preferably comprises triazole and / or triazole derivative and antioxidants in an amount of 0.1 to 5% by weight, based on the total weight of the relevant soft polyurethane. Suitable antioxidants are, in general, substances that inhibit or prevent unwanted oxidative processes in the plastic to be protected. In general, antioxidants are commercially available. Examples of antioxidants are sterically hindered phenols, aromatic amines, thiosynergists, trivalent phosphorus organophosphorus compounds and hindered amine light stabilizers. Examples of sterically hindered phenols are found in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Munich, 2001 ([1]), pages 98107 and page 116 - page 121. Examples of aromatic amines are found in [ 1], pages 107-108. Examples of thiosynergists are given in [1], pages 104-105 and pages 112-113. Phosphite examples are found on [1], pages 109-112. Examples of hindered amide light stabilizers are given in [1], pages 123-136. Phenolic antioxidants are preferably suitable for use in the antioxidant mixture. In a preferred embodiment, antioxidants, in particular phenolic antioxidants, have a molar mass greater than 350 g / mol, particularly preferably greater than 700 g / mol, and a maximum molar mass (Mw) of up to no more than 10,000 g / mol. mol, preferably up to no more than 3,000 g / mol. In addition, they preferably have a melting point of no more than 180 ° C. In addition, antioxidants that are amorphous or liquid are preferably used. Mixtures of two or more antioxidants can also be used as a component (e).

In addition to said components (a), (b) and (c) and, if appropriate, (d) and (e), it is also possible to use chain transfer agents (chain terminators), usually having a molecular weight of 31 to 3,000 g / mol. Such chain transfer agents are compounds that have only one functional group reactive with isocyanates, such as, for example, monofunctional alcohols, monofunctional amines and / or monofunctional polyols. Through such chain transfer agents, it is possible to establish flow behavior, in particular, in the case of soft polyurethanes, in a targeted manner. Chain transfer agents can be used, in general, in an amount of 0 to 5 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of component (b) and by definition are included in component (c).

In addition to said components (a), (b) and (c) and, if appropriate, (d) and (e), it is also possible to use crosslinking agents having two or more reactive groups with isocyanate towards the end of the reaction of synthesis, for example, hydrated hydrazine.

To establish the hardness of the polyurethane (A), the components (b) and (c) can be chosen in relatively broad molar ratios. Molar ratios of 10: 1 to 1: 10, in particular 1: 1 to 1: 4, of component (b) for chain extenders (c) to be used all together have proved to be useful, the hardness of the soft polyurethanes that increase with increasing content of (c). The reaction for the preparation of polyurethane (A) can be carried out at an index of 0.8 to 1.4: 1, preferably at an index of 0.9 to 1.2: 1, particularly preferably at an index of 1, 05 to 1,2: 1. The index is defined by the ratio of the isocyanate groups of component (a) that are used together in the reaction for the reactive groups with isocyanates, that is, the active hydrogens, of the components (b) and, if appropriate, (c) and, if appropriate, monofunctional components reactive with isocyanates, as chain terminators, such as, for example, monoalcohols.

The preparation of polyurethane (A) can be carried out by processes known per se, continuously, for example, by a firing process or the prepolymer process, or in batch by the prepolymer process known per se. In these processes, the components (a), (b), (c) and, if appropriate, (d) and / or (e) that react can be mixed with each other in succession or simultaneously, the reaction starting immediately.

Polyurethane (A) can be dispersed in water by methods known per se, for example, dissolving polyurethane (A) in acetone or preparing polyurethane (A) as a solution in acetone, adding water and then removing the acetone, for example, by distillation . In a variant, polyurethane (A) is prepared as a solution in N-methylpyrrolidone or Netylpyrrolidone, water is added and N-methylpyrrolidone or N-ethylpyrrolidone is removed.

In one embodiment of the present invention, aqueous dispersions according to the invention comprise two different polyurethanes (A ¹ ) and (A2), of which polyurethane (A ¹ ) is a so-called soft polyurethane, which has the composition as previously described for polyurethane (A), and at least one hard polyurethane (A2).

Hard polyurethane (A2) can, in principle, be prepared analogously to soft polyurethane (A ¹ ), but other compounds (b) reactive with isocyanates or other mixtures of compounds (b) reactive with isocyanates are chosen also designated in the context of the present invention. as compounds (b2) reactive with isocyanates or compound (b2) in short.

Examples of compounds (B2) are, in particular, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol, both as a mixture with one another and as a mixture with polyethylene glycol.

In a variant of the present invention, in each case, mixtures of diisocyanates are chosen as diisocyanates (a) and (a2), for example, mixtures of HDI and IPDI, higher proportions of IPDI being chosen for the preparation of hard polyurethane (A2) than for the preparation of soft polyurethane (A ¹ ).

In one embodiment of the present invention, polyurethane (A2) has a Shore A hardness in the range of more than 60 to no more than 100, the Shore A hardness being determined according to DIN 53505 after 3 seconds.

In one embodiment of the present invention, polyurethane (A) has an average particle diameter in the range of 100 to 300 nm, preferably 120 to 150 nm, determined by scattering laser light.

In one embodiment of the present invention, soft polyurethane (A ¹ ) has an average particle diameter in the range of 100 to 300 nm, preferably from 120 to 150 nm, determined by scattering laser light.

In one embodiment of the present invention, polyurethane (A2) has an average particle diameter in the range of 100 to 300 nm, preferably from 120 to 150 nm, determined by scattering laser light.

Aqueous dispersions according to the invention, furthermore, comprise (B) a compound of the general formula I a or I b, also referred to in the context of the present invention as compound (B) in summary,

O

Ia I b

3 where R, R and R can be different or preferably identical and are selected from A ^ NCO and A ^ NH-CO-X, where

A ¹ is a spacer having 2 to 20 carbon atoms, selected from arylene, unsubstituted or substituted by one to four C1-C4 alkyl, alkylene and cycloalkylene groups, for example, 1,4-cyclohexylene.

Preferred spacers A ¹ are phenylene, in particular para-phenylene, in addition, tolulene, in particular para-tolulene, and C2-C12 alkylene, such as, for example, ethylene (CH ₂ CH ₂ ), and in addition, - (CH ₂ ) 3-, - (CEb ^ -, - (CH ₂ ) 5-, (CH ₂ ) 6-, - (CH ₂ ) 8-, -CCH ₂ ) 10-, - (CH ₂ ) 12- .

X is selected from O (AO) _X R ⁴ , where

AO is C2-C4 alkylene oxide, for example, butylene oxide, in particular ethylene oxide (CH ₂ CH ₂ O) or propylene oxide (CH (CH ₃ ) CH ₂ O) or (CH ₂ CH (CH ₃ ) O), x is an integer in the range 1 to 50, preferably 5 to 25, and

R ⁴ is selected from hydrogen and C ₁ -C ₃ alkyl, in particular C 1 -C 10 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl , isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyla, noctila, 2-ethylhexyl, n-nonyl, n-decyl, particularly preferably C1- alkyl C4, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbutyl and tert-butyl.

Particularly preferred compounds (B) are those in which R ¹ and R ² and R ³ are, in each case, (CH ₂ ) 4-NCO, (CH ₂ ) 6-NCO or (CH ₂ ) i2-NCO.

Aqueous dispersions according to the invention, furthermore, comprise in each case (C) a silicone compound having reactive groups, also referred to in the context of the present invention as a silicone compound (C).

Examples of groups reactive with respect to silicone compounds (C) are, for example, carboxyl groups, carboxylic acid derivatives, such as, for example, methyl carboxylate or carboxylic anhydrides, in particular succinic anhydride groups and particularly preferably groups carboxyl.

Examples of reactive groups are, in addition, primary and secondary amino groups, for example, NH groups (iso-C ₃ H ₇ ), NH groups (n12

C ₃ H ₇ ), NH groups (cyclo-C ₆ Hn) and NH groups (nC ₄ H ₉ ), in particular NH groups (C ₂ H ₅ ) and NH groups (CH ₃ ) and most particularly preferably NH ₂ groups.

Aminoalkylamino groups, such as, for example, 5 NH-CH ₂ -CH ₂ -NH ₂ groups, - NH-CH ₂ -CH ₂ -CH ₂ -NH ₂ groups, -NH-CH ₂ -CH ₂ NH groups (C ₂ H ₅ ), -NH-CH ₂ -CH ₂ -CH ₂ -NH groups (C ₂ H ₅ ), -NH-CH ₂ -CH ₂ NH groups (CH ₃ ) and -NH-CH ₂ -CH _{2 groups} -CH ₂ -NH (CH ₃ ), are furthermore preferred. The reactive group or reactive groups is or is attached to the silicone compound (C) either directly or preferably via a spacer A2. A2 is selected from arylene, unsubstituted or substituted by one to four C 1 -C ₄ alkyl, alkylene and cycloalkylene groups, such as, for example, 1,4-cyclohexylene. Preferred A2 spacers are phenylene, in particular para-phenylene, in addition, tolulene, in particular para-tolulene, and C ₂ -C ₈ alkylene, such as, for example, ethylene (CH ₂ CH ₂ ), in addition,

- (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - <ch ₂ ) ₆ -, - (CH ₂ ) ₈ -, -cch ₂ ) ₁₀ -, - (CH ₂ ) ₁₂ -, (CH ₂ ) ₁₄ -, - (CH ₂ ) ₁₆ - and - (CH ₂ ) ₁₈ -.

In addition to the reactive groups of silicone compound (C) comprises no reactive groups, in particular di- Ci-Cio-SI0 ₂ groups , or phenyl-alkyl Ci-Cio-SI0 ₂ groups, in particular dimethyl-SiO ₂ groups, and optionally one or more Si (CH ₃ ) ₂ -OH groups or Si (CH ₃ ) _{3 groups} .

In one embodiment of the present invention, silicone compound (C) averages one to four reactive groups per molecule.

In a specific embodiment of the present invention, silicone compound (C) has on average one to four COOH groups per molecule.

In another specific embodiment of the present invention, silicone compound (C) averages from one to four amino groups or aminoalkylamino groups per molecule.

Silicone compound (C) has Si-O-Si units arranged in the form of chains or in the branched form.

In one embodiment of the present invention, silicone compound (C) has a molecular weight Mn in the range of 500 to 10,000 g / mol, preferably up to 5,000 g / mol.

If the silicone compound (C) has a plurality of reactive groups per molecule, these reactive groups can be linked - directly or via the A2 spacer - via a plurality of Si atoms or in pairs via the same Si atom to the Si-O-Si chain.

Reactive groups or reactive groups can be attached to one or more of the Si terminal atoms of the silicone compound (C) directly or by means of a spacer A2. In another embodiment of the present invention, the reactive group is or the reactive groups are attached to one or more of the non-terminal Si atoms of silicone compound (C) directly or via the A2 spacer.

In one embodiment of the present invention, the aqueous dispersion according to the invention comprises (D) a C1-C4 polydialkylsiloxane that has neither amino groups nor COOH groups, preferably a polydimethylsiloxane, also referred to in the context of the present invention as polydialkylsiloxane (D ) and polydimethylsiloxane (D), respectively, in summary.

C1-C4 alkyl in polydialalkylsiloxane (D) can be different or preferably identical and can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, C1-C4 alkyl straight being preferred and methyl being particularly preferred.

Polydialkylsiloxane (D) and preferably polydimethylsiloxane (D) are preferably straight chain polysiloxanes having Si-O-Si chains or polysiloxanes having up to 3 branches, preferably no more than one branch per molecule.

Polydialkylsiloxane (D) and, in particular, polydimethylsiloxane (D) can have one or more Si groups (C 1 -C 4 alkyl-OH).

In an embodiment of the present invention, the aqueous dispersion according to the invention comprises together in the range of 20 to 30% by weight of polyurethane (A) or together in the range of 20 to 30% by weight of polyurethanes (A ¹ ) and (A2), in the range of 1 to 10, preferably from 2 to 5,% by weight of compound (B), in the range of 1 to 10% by weight of silicone compound (C), in the range of zero to 5, preferably from 2 to 4,% by weight of crosslinking agent (D), in the range of zero to 10, preferably from 0.5 to 5,% by weight of polydialkylsiloxane (D).

The data in% by weight designates in each case the active or solid substance and is based on the total aqueous dispersion according to the invention. The remaining 100% by weight is preferably a continuous phase, for example, water or a mixture of one or more organic solvents and water, at least 50% by weight being water in the aforementioned mixtures. Suitable organic solvents are, for example, alcohols, such as ethanol or isopropanol and, in particular, glycols, diglycols, triglycols or tetraglycols and glycols, diglycols, triglycols or tetraglycols dieterified or preferably monoeterified with C1-C4 alkyl. Examples of suitable organic solvents are ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,2-dimethoxyethane, methyltriethylene glycol ("methyltriglycol") and n-butyl triethylene glycol ("butyltriglycol" ”).

In an embodiment of the present invention, the aqueous dispersion according to the invention comprises in the range of 10 to 30% by weight of soft polyurethane (A ¹ ) and in the range of zero to 20% by weight of hard polyurethane (A2).

In an embodiment of the present invention, the aqueous dispersion according to the invention has a solids content of from 5 to 60% by weight, preferably from 10 to 50% by weight and particularly preferably from 25 to 45% by weight.

In an embodiment of the present invention, aqueous dispersion according to the invention comprises at least one additive (E), selected from pigments, glare agents, light stabilizers, antistatic agents, anti-soil agents, anti-breakage agents, thickeners, in particular , thickeners based on polyurethanes, and hollow microspheres.

In an embodiment of the present invention, the aqueous dispersion according to the invention together comprises up to 20% by weight of additives (E).

In addition, a process for the preparation of aqueous dispersions according to the invention has been found, also referred to in the context of the present invention as the preparation process according to the invention. To carry out the preparation process according to the invention, polyurethane (A), compound (B) and silicone compound (C) are mixed with water and optionally one or more of the aforementioned organic solvents. In addition, if desired, mixing with polydialkylsiloxane (D) and additives (E) is carried out. The mixing can be carried out, for example, by stirring. The sequence of addition of polyurethane (A), compound (B), silicone compound (C) and water and optionally one or more of the organic solvents mentioned above and - if desired - polydialkylsiloxane (D) and additives (E) is arbitrary.

A polyurethane (A) dispersed in water or a mixture of water and organic solvent or soft dispersed polyurethane (A ¹ ) and hard polyurethane (A2) is preferably used as a starting material, and compound (B) and silicone compound (C ) and, if desired, polydialkylsiloxane (D) and optionally one or more organic solvents are added, preferably with stirring.

In a specific embodiment of the preparation process according to the invention, a thickener, as an example of an additive (E), is added last and the desired viscosity is thus established.

The present invention, moreover, concerns the use of aqueous dispersions according to the invention for the production of multilayer sheet-like substrates. The present invention, moreover, relates to a process for the production of multilayer sheet-like substrates using aqueous dispersions according to the invention, also referred to in the context of the present invention as a coating process according to the invention. The present invention, moreover, relates to multilayered sheet-like substrates produced using aqueous dispersions according to the invention.

For the production of multilayer sheet-like substrates according to the invention, sheet-like substrates are used as starting materials. Sheet-like substrates can be, for example, plastic films, for example, comprising polyethylene, polypropylene, polyester, polycarbonate, polystyrene or polyvinyl chloride. Leaf-like substrates are preferably selected from textiles, for example, mats, knitted fabrics, wefts, nets, knitwear, woven cloths and, in particular, non-woven, synthetic suede materials having a top consisting of microfibers. Additional suitable sheet-like substrates are molds comprising plastic, for example, panels, in addition, imitation leather and very particularly preferably leather, leather also including leather sliver and leather having rawhide defects. Leather can be tanned by any method, for example, with chromium (III) compounds or in the absence of chromium, and can be attributed to any animal skin, in particular to cattle. It is not important if the animal whose leather skin used in the process according to the invention was prepared was euthanized or died of accidental or natural causes, for example, diseases.

If it is desired to use leather as a leaf-like substrate, the meat or fur side can be coated with dispersion according to the invention.

In one embodiment of the present invention, sheet-like substrate is coated with dispersion according to the invention and then curing is carried out, for example, by heat treatment.

In a preferred embodiment of the present invention, the sheet-like substrate is coated by a reverse roller coating process, as described, for example, in WO 05/47549.

In a particularly preferred embodiment of the present invention, the following procedure is adopted. In a first step, a sheet-like body is produced from a material, preferably metal, plastic or in particular a silicone, in particular a silicone rubber. In a second step, a structure is given to the sheet-like body, for example, by marking and, preferably, by treatment with the help of a laser. The structure preferably corresponds to the structure of the leather of a leather, for example, leather of a cattle, calf or crocodile or to the surface structure of a Nubuck leather. In a variant of the present invention, the structure can have a fancy structure or logos can be produced by marking.

In a specific embodiment, the structure not only has the structure of a leather coat, for example, leather of a cattle, calf or crocodile, but additionally fine carvings having a maximum depth of 200 pm, preferably from 60 to 100 pm, and an average diameter in the range of 10 to 30 pm. The pattern of the carvings can then correspond to the leather of a cattle, calf or crocodile.

In one embodiment of the present invention, the sheet-like body has a thickness in the range of 0.5 to 5 mm, preferably 1 to 3 mm.

In the third stage of the coating process, according to the invention, a procedure is preferably adopted in which aqueous dispersion according to the invention is applied to the structured body, for example, by spraying, spraying, pouring, knife coating, coating or roller coating.

For example, from 10 to 100 g / m2, preferably from 50 to 75 g / m2, the aqueous dispersion according to the invention can be applied to the sheet-like body.

In one embodiment of the present invention, the sheet-like body is at room temperature. Preferably, however, it is at a temperature that is higher than the ambient temperature, in particular in the range of 35 to 90 ° C. Further solidification of the coating by aqueous dispersion according to the invention is carried out.

In a fourth step, the solidified coating is then transferred to a sheet-like substrate. The transfer can be carried out manually or preferably mechanically, in particular in such a way that the sheet-like body is connected to a cylinder or roller, and the coating is now transferred to the relevant sheet-like substrate with the help of the sheet-like body applied to a cylinder or roll. A multilayer substrate according to the invention is obtained. The solidified coating produced from the aqueous dispersion according to the invention serves as a top layer on the multilayer substrate according to the invention and, in the context of the present invention, can also be referred to as the top layer.

In an additional step, the adhesion of the transferred layer and sheet-like substrate can also be improved by thermally treating or compressing the newly produced multilayer substrate according to the invention or by performing a combination of the previously mentioned steps.

It is observed that, when carrying out the coating process according to the invention, the sheet-like body declines in quality only extremely slowly, for example, as a result of stain formation.

Multilayer substrates according to the invention have advantageous properties as a whole, for example, good breathability, very good firmness during use, such as, for example, friction firmness and very good handling.

In a preferred embodiment of the present invention, the coating produced using the aqueous dispersion according to the invention is not transferred directly to the sheet-like substrate, but another bonding layer is first applied to the solidified coating, as long as it still presents in the sheet-like body, for example, the cylinder or roller, and the coating produced using the aqueous dispersion according to the invention and the bonding layer are transferred together to the sheet-like substrate.

In a particularly preferred embodiment of the present invention, the coating produced using the aqueous dispersion according to the invention is not transferred directly to the sheet-like substrate, but a bonding layer is first applied to the solidified coating, as long as it is still present on the body, and a second bonding layer is applied to the sheet-like substrate, the two bonding layers having substantially the same composition, and the coating produced using the aqueous dispersion according to the invention and the bonding layer are transferred together to the sheet-like substrate already supplied with the bonding layer.

The bonding layer or bonding layers having substantially the same composition are, for example, layers that are obtained by applying preferably one or more aqueous formulations, the relevant aqueous formulations having the following composition:

(a) at least one polyurethane, which can be identical or different from polyurethane (A), (β) at least one compound of the general formula I a or I b, which is defined as above, also referred to as compound (β) in abstract; compound (B) and compound (β) are preferably identical, (γ) preferably at least one binder, for example, a (meth) acrylate, binder or a polyurethane binder, preferably a (meth) acrylic acid copolymer, also referred to in the context of the present invention as a binder (γ). Binder (γ) is preferably a (meth) acrylic acid copolymer and at least one (meth) acrylic acid C1-10 alkyl ester (δ) if appropriate, at least one additive, for example, selected from pigments, agents handling agents, thickeners, antistatic agents and glare agents.

The remainder is preferably water.

Preferably, the aqueous formulation or aqueous formulations from which it is desired to produce the top layer (s) comprise or comprise a silicone compound, such as, for example, silicone compound (C), or such as polydialkylsiloxane (D).

In one embodiment of the present invention, the aqueous formulation or aqueous formulations from which it is desired to produce the top layer (s) comprise or comprise at least one soft polyurethane (al) and at least one hard polyurethane (a2), which in each can be different or preferably identical to soft polyurethane (A ¹ ) or hard polyurethane (A2).

The aqueous formulation or aqueous formulations from which it is desired to produce the upper layer (s) may comprise one or more organic solvents. Examples of organic solvents are alcohols, such as ethanol or isopropanol, and in particular glycols, diglycols, triglycols or tetraglycols and glycols, diglycols, triglycols or tetraglycols dieterified or preferably monoeterified with C1-C4 alkyl. Examples of suitable organic solvents are ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,2dimethoxyethane, methyltriethylene glycol ("methyltriglycol") and triethylene glycol ("butyltriglycol").

In one embodiment of the present invention, the aqueous formulation or aqueous formulations from which it is desired to produce the upper layer (s) have or have the following composition:

together in the range of 20 to 30% by weight of polyurethane (a), in the range of 1 to 5, preferably from 2 to 3,% by weight of the compound (β), in the range of up to 20% by weight of binder ( γ), in the range of zero to together 20% by weight of additive (s) (δ), and preferably neither the silicone compound (C) nor polydialalkylsiloxane (D).

In an embodiment of the present invention, the aqueous formulation or aqueous formulations for which it is desired to produce the top layer (s) comprise or comprise in the range of 10 to 30% by weight of soft polyurethane (al) and in the range of zero to 20% by weight of hard polyurethane (a2).

The data in% by weight designates, in each case, the active substance or solid and is based on the total aqueous formulation used in the coating process according to the invention. The remaining 100% by weight is preferably a continuous phase, for example, water or a mixture of one or more organic solvents and water, at least 50% by weight of water being present in the aforementioned mixtures.

The thickness of the upper layers can be in the range of 5 to μηι, preferably from 10 to 30 pm.

The application can be carried out, for example, by spraying, spraying, pouring, knife coating, coating or roller coating.

The bonding of the layers can be improved or accelerated by routine methods, for example, by heat treatment and from 80 to 120 ° C and / or by pressing together with a contact pressure in the range of 1 to 3 bar.

Multilayer substrates according to the invention are suitable for the production of, for example, furniture parts and, in particular, car interior panels, in particular, car seats and, in addition, shoes, textiles and furniture parts. furniture. They have good firmness and, in addition, excellent breathability. The present invention, therefore, moreover, concerns interior panels of automobiles, shoes, textiles and pieces of furniture, produced using multilayer substrates according to the invention.

The invention is illustrated by working examples.

General observation: data in% by weight are as they are.

I. Preparation of aqueous dispersions according to the invention

1.1 Preparation of an aqueous dispersion Disp.l according to the invention.

The following were mixed in a stirred vessel with stirring:

% by weight of an aqueous dispersion (particle diameter: 125 nm, solids content: 40%) of a soft polyurethane (A 1.1), prepared with hexamethylene diisocyanate (A 1.1) and isophorone diisocyanate (A 1.2) in the ratio by weight 13:10 as diisocyanates and, as diols, a polyesterdiol (bl.l) having a molecular weight Mw of 800 g / mol, prepared by polycondensation of isophthalic acid, adipic acid and 1,4 dihydroxymethylcyclohexane (mixture of isomers) in a molar ratio of 1: 1: 2,% by weight of 1,4-butanediol (bl.2) and 3% by weight of monomethylated polyethylene glycol (cl) and 3% by weight of H ₂ N-CH2CH2-NH-CH ₂ CH ₂ -COOH,% by weight in each case based on polyesterdiol (bl.l), Soft polyurethane softening point (A ¹ !): 62 ° C, softening starts at ° C, Shore A 54 hardness, % by weight of an aqueous dispersion (particle diameter: 150 nm) of a hard polyurethane (A2.1), obtainable by reacting isophorone diisocyanate (A ¹ .2), 1,4-butanediol (bl.2) and H ₂ N-CH ₂ CH ₂ -NH-CH ₂ CH ₂ -COOH, am 195 ° C, Shore A 86 hardness,

3.5% by weight of a 70% by weight solution (in propylene carbonate) of the compound (B.l)

JCH ₂ ) ₆ NCO ° ^ ^N ^ °

Γ (B .1)

OCN-ICH,) ^ γ ^ (CH ₂ ) ₆ NCO The NCO content 12%,% by weight of 65% by weight of the aqueous dispersion of the silicone compound according to example 2 of EP-A 0 738 747 ( Cl),% by weight of carbon black,

0.5% by weight of a polyurethane based thickener.

Aqueous dispersion Disp.l according to the invention was obtained with a solids content of 35% and a kinematic viscosity of 25 seconds at 23 ° C, determined according to DIN EN ISO 2431, effective date May 1996.

1.2 Preparation of an aqueous dispersion Disp.2 according to the invention

The following were mixed in a stirred vessel with stirring:

% by weight of an aqueous dispersion (particle diameter:

125 nm, solids content: 40%) of a soft polyurethane (A ^1. !), Prepared from hexamethylene diisocyanate (A \ l) and isophorone diisocyanate (A ¹ .2) in the 13:10 weight ratio as diisocyanates and, as diols, a polyesterdiol (bl.l) having a molecular weight Mw of 800 g / mol, prepared from polycondensation of isophthalic acid, adipic acid and 1,4 dihydroxymethylcyclohexane (mixture of isomers) in a molar ratio of 1: 1 : 2.5% by weight of 1,4-butanediol (bl.2), and 3% by weight of monomethylated polyethylene glycol (cl) and 3% by weight of H ₂ N-CH ₂ CH ₂ -NH-CH ₂ CH ₂ -COOH,% by weight in each case based on polyesterdiol (bl.l), Soft polyurethane softening point (A ^1. ): 62 ° C, softening starts at 55 ° C, Shore A 54 hardness, % by weight of an aqueous dispersion (particle diameter: 150 nm) of a hard polyurethane (A2.2), obtainable by reacting isophorone diisocyanate (A ¹ .2), 1,4-butanediol (bl.2), acid 1 , 1-dimethylolpropionic, hydrazine hydrate and polypropylene glycol having a molecular weight 4200 g / mol (bl.3) Mw air, polyurethane (A2.2) had a softening point of 195 ° C, Shore A 86 hardness,

3.5% by weight of a 70% by weight solution (in propylene carbonate) of the compound (Bl),% by weight of 65% by weight of the aqueous dispersion of the silicone compound according to example 2 of EP-a 0 738 747 (Cl),% by weight of carbon black,

0.5% by weight of a polyurethane based thickener.

Aqueous dispersion Disp.2 according to the invention was obtained with a solids content of 35% and a kinematic viscosity of 25 seconds at 23 ° C, determined according to DIN EN ISO 2431, effective date of May 1996.

II. Production of a sheet-like body

A laser-engravable silicone polymer having a smooth surface and based on a 2-component silicone elastomer containing curing charge at room temperature was produced by thoroughly mixing the two components with one another and applying them with the help of coating with knife to a temporary PET cover sheet. The silicone layer healed naturally for 16 hours at room temperature. The chemically reinforced elastomeric silicone layer in this way was fixed with the help of a silicone adhesive on a cloth polyester fabric as a carrier element. The elastomeric polymer layer reinforced with cloth fabric carrier, obtained after the removal of the temporary PET cover sheet, had a total layer thickness of 1.7 mm. The obtained leaf type body (unstructured) was converted into leaf segments measuring about 40 x 100 cm before the subsequent structuring by means of a laser.

For structuring the sheet-like body, a machine that engages with CO ₂ laser type BDE 4131 (from Stork Prints Austria GmbH, Kufstein) was used. The machine has 3 sealed CO ₂ lasers having an estimated power of 250 W each, the corresponding optical components and associated peripherals for control, laser cooling, exhaust air collection and exhaust air treatment. The cylindrical registration system consisted of both a thin-walled cylindrical metal drum and metal cones in which a so-called printing sleeve, consisting of a hollow cylindrical cylinder (usually composed of a plurality of layers) comprising one or more plastics, is stapled. The control of the laser was carried out by means of a control computer connected by means of special output software. The output software interprets the motif, present as a gray gradation bitmap, as a pixel-by-pixel height profile. Each gray-colored graduation corresponds to a certain notched depth or notch force at the relevant point of the subject. Ideally, the relationship between gray color graduation value and notch depth is adjusted to be approximately linear.

The sheet-like body (unstructured) was presented as a planar layer and was fixed to a cylindrical support element for the duration of the notch. During the notching process, the rotating cylindrical support element with the die to be processed was moved uniformly with respect to the laser beam in the axial direction. In this way, the laser beam passed over the entire surface of the sheet-like body, the surface of which will be processed.

The sheet body (unstructured) according to example

II. it was carved with a pattern that consisted of a combination of the following two individual motifs according to table 1.

Table 1: Individual motifs of the motif in the leaf type body (structured)

Individual reason no. Occupation reason type 1 wells wells with Diameter = 72 pm center-to-center distance = 100 pm (in the form of an inverted halftone screen of 100 1 / cm = 254 lpi at a tone value of 40%) 2 micro-roughness roughness pattern roughness amplitude = 30 pm roughness frequency = 30 pm

lpi = lines per inch

In this way, a sheet-like body (structured) having a rough surface and about 10,000 wells / cm2 was obtained. The depth of the carved wells was about 80 pm. The sheet-like (structured) body was subsequently cleaned with the help of a water-surfactant mixture and used directly for the coating process according to the invention.

III. Preparation of aqueous formulations for the top layer

III. 1 Preparation of an aqueous formulation AF.l according to the invention

The following were mixed in a stirred vessel with stirring:

% by weight of an aqueous dispersion (particle diameter: 125 nm), solids content: 40%) of a soft polyurethane (al.l), prepared from hexamethylene diisocyanate (A \ l) and isophorone diisocyanate (A ¹ .2) in the 13:10 weight ratio as diisocyanates and, as diols, a polyesterdiol (bl.l) having a molecular weight Mw of 800 g / mol, prepared from polycondensation of isophthalic acid, adipic acid and 1,4 dihydroxymethylcyclohexane (mixture of isomers) in a molar ratio of 1: 1: 2, 5% by weight of 1,4-butanediol (bl.2), 3% by weight of monomethylated polyethylene glycol (cl) and 3% by weight H2N-CH2CH2- NH-CH2CH2-COOH,% by weight in each case based on polyesterdiol (bl.l), Softening point of 62 ° C, softening starts at 55 ° C, Hardness Shore A 54,% by weight of an aqueous dispersion ( particle diameter: 150 nm) of a hard polyurethane (a2.1), obtainable by reacting isophorone diisocyanate (A ¹ .2), 1,4-butanediol (bl.2) and H2N-CH2CH2-NH-CH2CH2-COOH, softening point of 170 ° C, Shore A 90 hardness,

3.5 wt% of a 70 wt% solution (in propylene carbonate) of the compound (β. 1), 12% NCO content, wt% carbon black.

Aqueous formulation AF.l was obtained.

observation: compound (B.l) was identical to compound (β.1).

III.2 Preparation of an aqueous formulation AF.2 according to the invention

The following were mixed in a stirred vessel with stirring:

% by weight of an aqueous dispersion (particle diameter:

125 nm), solids content: 40%) of a soft polyurethane (al.l), prepared from hexamethylene diisocyanate (A ^1. !) And isophorone diisocyanate (A ¹ .2) in the 13:10 weight ratio as diisocyanates and, as diols, a polyesterdiol (bl.l) having a molecular weight Mw of 800 g / mol, prepared from polycondensation of isophthalic acid, adipic acid and 1,4 dihydroxymethylcyclohexane (mixture of isomers) in a molar ratio of 1: 1 : 2.5% by weight of 1,4-butanediol (bl.2), 3% by weight of monomethylated polyethylene glycol (cl) and 3% by weight H ₂ N-CH ₂ CH ₂ -NH-CH ₂ CH ₂ -COOH,% by weight in each case based on polyesterdiol (bl.l), Softening point of 62 ° C, softening starts at 55 ° C, Shore A hardness 54,% by weight of an aqueous dispersion (particle diameter : 150 nm) of a hard polyurethane (a2.2), obtainable by reacting isophorone diisocyanate (A ¹ .2), 1,4-butanediol (bl.2), 1,1-dimethylolpropionic acid, hydrazine hydrate and polypropylene glycol having an Mw molecular weight of 4,200 g / mol (bl.3), polyur ethane (a2.2) weaves a softening point of 195 ° C, Shore A 90 hardness,

3.5 wt% of a 70 wt% solution (in propylene carbonate) of the compound (β. 1), 12% NCO content, wt% carbon black.

The aqueous dispersion AF.2 according to the invention was obtained with a solids content of 35% and a kinematic viscosity of 25 sec determined at 23 ° C according to DIN EN ISO 2431, effective date of May 1996.

IV. Application of dispersions according to the invention to II-type bodies.

The sheet-like body was placed on a heatable surface and heated to 80 ° C. Thus, Disp.l or Disp.2 was blasted by a plurality of spray nozzles, in each case 60 g / m (wet). Solidification occurred naturally at 80 ° C until the surface was no longer sticky. A sheet-like body coated with an upper layer was obtained.

V. Application of a bonding layer to leather and to IV sheet-like bodies that have been coated with a top layer and application of coatings of the sheet-like body to leather.

AF.l or AF.2 was applied, at 70 g / m (wet), by means of 2 spray nozzles analogously to IV to the IV-type body which was coated with an upper layer. The drying took place naturally in an air dryer at 80 ° C until the surface was no longer sticky. A sheet-like body coated with an upper layer and a bonding layer was obtained.

AF.l or AF.2 was applied with the aid of a spray gun to the leather of nappa leather conventionally tanned with chromium (III), in an amount of 50 g / m (wet). Storage was carried out for two minutes at room temperature, after which the coated cattle leather felt dry.

The coated cattle nappa leather was then placed with the coating side down on the sheet-like body coated with an upper layer and a bonding layer and pressing was carried out in a hot press (90 ° C) with the help of elastic pressure supports at a pressure of 2 bar for a period of 15 seconds. An L.l coated cattle nappa leather according to the invention was obtained.

The sheet-like body (uncoated) can be easily and completely removed from the coated cattle leather L. 1 or L.2 according to the invention and used again immediately.

Leather napkins L.l and L.2 according to the invention had the following properties:

Adhesive strength based on DIN EN ISO 11644 with a cyanoacrylate adhesive: dry value: 21.3 N / cm, wet value: 10.3 N / cm or

10.5 N / cm

Friction stability based on DIN EN ISO 11640:

Friction stability with gasoline, tested with petroleum ether: rate 5 per 20 x

Friction stability with mild soap: rate 5 per 100 x

Friction stability with solvent, tested with ethanol: rate 5

Friction stability with humidity, rate 4 to 5 per 500 x

Friction stability with perspiration: rate 5 per 100x

Dry friction stability: rate 5 per 2,000 x

SAW. Non-woven coating

A non-woven (polyester) and a sheet-like body (structured) according to II were used as starting materials.

SAW. 1 Preparation of aqueous dispersions Disp.3 and Disp.4 according to the invention

The following were mixed in a stirred vessel with stirring:

% by weight of an aqueous dispersion (particle diameter: 125 nm) of a thermoplastic polyurethane (A ^ l), prepared from hexamethyl diisocyanate (A 1.1) and isophorone diisocyanate (A ¹ .2) in weight ratio 13: 10 as diisocyanates and, as diols, a polyester diol (bl.l) having a molecular weight Mw of 800 g / mol, prepared from polycondensation of isophthalic acid, adipic acid and 1,4-dihydroxymethylcyclohexane (mixture of isomers) in a ratio molar 1: 1: 2, 5% by weight of 1,4-butanediol (bl.2), 3% by weight of monomethylated polyethylene glycol (cl) and 3% by weight of H ₂ NCH ₂ CH ₂ -NH- CH ₂ CH ₂ -COOH,% by weight in each case based on polyesterdiol (bl.l), softening point of 62 ° C, softening starts at 55 ° C, Shore A hardness 54,% by weight of an aqueous dispersion (particle diameter: 150 nm) of a hard polyurethane (A 1.2), obtainable by reacting isophorone diisocyanate, 1,4-butanediol and H ₂ N-CH ₂ CH ₂ -NH-CH ₂ CH ₂ -COOH, Shore A hardness 86,

3.5% by weight of a 70% by weight solution (in propylene carbonate) of the compound (Bl) (see above), 12% NCO content,% by weight of a 60% by weight of the aqueous dispersion of the compound of silicone according to example 2 of EP-A 0 738 747 (Cl), wt% carbon black,

0.5% by weight of a polyurethane based thickener,% by weight of hollow microspheres, average diameter 20 pm, comprising polyvinylidene chloride, loaded with isobutane,% by weight of silica gel.

Aqueous dispersion Disp.3 according to the invention was obtained with a solids content of 30% and a kinematic viscosity of 25 seconds at 23 ° C, determined in accordance with DIN EN ISO 2431, effective date of May 1996.

The following were mixed in a stirred vessel with stirring:

% by weight of an aqueous dispersion (particle diameter: 125 nm) of a thermoplastic polyurethane (A \ l), prepared from hexamethyl diisocyanate (A \ l) and isophorone diisocyanate (A ¹ .2) in weight ratio 13 : 10 as diisocyanates and, as diols, a polyester diol (bl.l) having a molecular weight Mw of 800 g / mol, prepared from polycondensation of isophthalic acid, adipic acid and 1,4-dihydroxymethylcyclohexane (mixture of isomers) in a molar ratio of 1: 1: 2, 5% by weight of 1,4-butanediol (bl.2), 3% by weight of monomethylated polyethylene glycol (cl) and 3% by weight of H ₂ NCH ₂ CH ₂ -NH -CH ₂ CH ₂ -COOH,% by weight in each case based on polyesterdiol (bl.l), softening point of 62 ° C, softening starts at 55 ° C, Shore A hardness 54,% by weight of a dispersion aqueous (particle diameter:

150 nm) of a hard polyurethane (A2.2), obtainable by reacting isophorone diisocyanate, 1,4-butanediol, 1,1-dimethylolpropionic acid, hydrazine hydrate and polypropylene glycol having a molecular weight Mw of 4200 g / mol, dot 195 ° C softening, Shore A 86 hardness,

3.5% by weight of a 70% by weight solution (in propylene carbonate) of the compound (Bl) (see above), 12% NCO content,% by weight of a 60% by weight of the aqueous dispersion of the compound of silicone according to example 2 of EP-A 0 738 747 (Cl), wt% carbon black,

0.5% by weight of a polyurethane based thickener,% by weight of hollow microspheres, average diameter 20 pm, comprising polyvinylidene chloride, loaded with isobutane,% by weight of silica gel.

Aqueous dispersion Disp.4 according to the invention was obtained with a solids content of 30% and a kinematic viscosity of 25 seconds at 23 ° C, determined according to DIN EN ISO 2431, effective date of May 1996.

VI.2 Application of dispersions according to the invention to II-type bodies.

The leaf-like body of II. was placed on a surface that can be heated and heated to 80 ° C. Disp.3 or Disp.4 was then blasted using a plurality of spray nozzles, at 80 g / m2 (wet). Solidification occurred naturally at 80 ° C until the surface was no longer sticky. Sheet-like bodies coated with an upper layer were obtained.

AF. l or AF.2 was applied with spray nozzles similarly to V. to VI leaf type bodies. which have been coated with an upper layer, in each case 50 g / m2 (wet). Drying took place naturally in an air dryer at 80 ° C until the surface was no longer sticky. Sheet-like bodies coated with an upper layer and a bonding layer were obtained.

AF.l or AF.2 was applied to a nonwoven in each case 50 g / m2 (wet). Storage was carried out for two minutes at room temperature, after which the coated nonwovens felt dry.

Thereafter, the coated nonwovens were placed with the coating side down on the sheet-like bodies coated with an upper layer and a bonding layer and were pressed in a heated press (90 ° C) with the help of elastic supports of pressure at a pressure of 2 bar for a period of 15 seconds. Non-woven coated

NW. 1 and NW.2 according to the invention were obtained.

The sheet-like body (uncoated) can be easily and completely removed from NW.l or NW.2 coated nonwovens according to the invention and used again immediately. NW.l and NW.2 nonwovens coated according to the invention were elastic, breathable and dimensionally stable and had very good handling.

Claims (11)

1. Aqueous dispersion, characterized by the fact that it comprises (A) at least one polyurethane, (B) at least one compound of the general formula I a or I b O. R I, N. ΥΎ Y R I, N. ° γ ^Ν γ °, NH HI \ L „, 3 / ' Ia I b where R ¹ , R ² and R ³ can be identical or different and are selected from A '-NCO and Α'-ΝΗ-CO-X, where A ¹ is a spacer having 2 to 20 carbon atoms and X is selected from O (AO) _X R ⁴ , AO is C2-C4 alkylene oxide, x is an integer in the range 1 to 50 and R ⁴ is selected from hydrogen and C1-C30 alkyl, and at least one silicone compound having reactive groups, wherein the silicone compound (C) is selected from silicone compounds having one to four amino groups per molecule, silicone compounds having one to four aminoalkylamino groups per molecule and silicone compounds having one to four COOH groups per molecule. 2. Aqueous dispersion according to claim 1, characterized by the fact that AO is selected from ethylene oxide and propylene oxide. Aqueous dispersion according to claim 1 or 2, characterized in that it additionally comprises (D) at least one C1-C4 polydylalkyloxane which does not have Petition 870180026801, of 03/04/2018, p. 9/12 neither amino groups nor COOH groups. Aqueous dispersion according to any one of claims 1 to 3, characterized in that A ¹ is selected from phenylene, toluylene and C2-C12 alkylene. 5. Use of aqueous dispersions, as defined in any of claims 1 to 4, characterized by the fact that it is for the production of multilayered sheet-like substrates. 6. Process for the production of multilayer sheet-like substrates, characterized by the use of aqueous dispersions, as defined in any one of claims 1 to 4. 7. Process according to claim 6, characterized by the fact that a sheet-like body is produced from a silicone in a first stage and is provided with a structure in a second stage, aqueous dispersion, as defined in any of the claims 1 to 4 is applied to the structured body in the third step and the layer from the steps mentioned above is transferred to a sheet-like substrate in a fourth step. 8. Multilayer sheet-like substrate, characterized by the fact that it is produced by a process, as defined in claim 6 or 7. 9. Multilayer sheet-like substrate according to claim 8, characterized by the fact that the sheet-like substrate is selected from plastic films, leather, imitation leather, textiles and molds comprising plastic. 10. Use of multilayered sheet-like substrates, as defined in claim 8 or 9, characterized by the fact that it is for the production of automobile interior panels, shoes, textiles and furniture pieces. 11. Interior panels for cars, shoes, textiles or garments Petition 870180026801, of 03/04/2018, p. 10/12 furniture, characterized by the fact that they are produced using multilayered sheet-like substrates, as defined in claim 8 or 9. Petition 870180026801, of 03/04/2018, p. 12/11